DE2654882A1 - PHOTOGRAPHIC SILVER HALOGENIDE EMULSIONS AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

PATENT LAWYERS

Dipl.-Ing. P. WIRTH Dr. V. SCH MI ED-KOWARZIK Dipl.-Ing. G. DAN N EN BERG ■ Dr. P. WEINHOLD ■ Dr. D. GUDEL

TELEPHONE (0611)

281134 287014

6 FRANKFURTAM MAIN

GR. ESCHENHEIMER STRASSE 38

Gases i PM-800 Y / d / kg

GAi ¹ Corporation 140 West 51Bt Street, New York, New York United States of America

Silver halide photographic emulsions as well as procedures too. their manufacture

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265AS82

The invention relates to photographic silver! \ logenide emulsions, in particular on photographic emulsions of light-sensitive silver halides in an amphoteric copolymer.

Gelati »'■ which has been in industrial for the past 100 years Maßsta., 1 as a binder for the silver halide crystals in photographic emulsions have been used plays an important role in generating the sensitometric

Specially "ι mass > and ^loading! Increased lights haloge" sizes barei ^ correct ί unstable by ν cheniisV emulsi ^v , shaft-steep

laften as they act as a peptizer and as a protective Ir the crystals work and the essential characteristics: and parts that are necessary to give the grains a To impart photosensitivity, can provide sensitivity, contrast and graininess of silver .demulsions are mainly determined by the size and division of the silver halide grains and by the

of the grains to chemical sensitization with be-ι Corabinations of sensitizers, such as

> sulfur

and gold compounds, definitely "

Controlling the crystal sizes properly

and the

That

system " ¹

minimal means hydroxL Krista ^ (e.g. i die ve Es is1ö one

With sensitization it is possible to produce photographic images with a variety of sensitometric properties and photographic applications

3tall growth in photographic gelatin emulsionsi is achieved through the use of high mixing temperatures (° C), long silver nitrate addition times (e.g. 1 hour), 2n gelatin concentrations, silver halide solution

(e.g. with high halide:! excess of ions or ammonium-1) accelerated; on the other hand, it is delayed when the Le is in the presence of certain divalent cations i) or slowing substances (e.g. nucleic acids), Naturally present in gelatin, relatively easy, photographic gelatin emulsions are formed using ride to manufacture crystal size distribution; it is

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but more difficult to get a narrow size distribution (in the absence of solvents such as ammonium hydroxide), especially when large crystals (i.e., more than 1 µm in average diameter) are desired. Commercially available polymers used as gelatin replacement materials have been proposed have not been found to be entirely satisfactory for controlling crystal growth. In most cases the materials are not effective peptizers and will not prevent clumping or clusters of crystals. Polymers such as polyvinyl alcohol, Polyacrylamide or polyvinylpyrrolidone, inhibit the growth of the grains so strongly that it is not possible Obtain silver halide crystals of sufficient size to have the desired sensitometric properties reach. Therefore, there is a need in the art for a gelatin substitute that provides crystal size control and that allows for distribution of sizes.

Also, the synthetic gelatin substitute should be so be that it can be produced with consistent physical, chemical and photographic properties, because Gelatine is a natural product and therefore its properties often vary from time to time.

The object of the present invention is therefore to provide a photographic silver halide emulsion based on a synthetic binder for the silver halide grains, at which the crystal size and the crystal size distribution of the silver halide grains can be controlled.

The present invention provides a photographic silver halide emulsion which is characterized in that the emulsion binder comprises a water-soluble, film-forming, amphoteric copolymer which is in the molecule repeating units of the general formula?

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■ on white. , in which

η * = .'a positive integer of preferably about 20 - ^ 000;

\ ■. ■.

R = ban residue of an ethylenically unsaturated organic

Monc, eren; ■; . '-. ■ "_.- ■ ·. ·' ·

X = ^ -, -S- or -0-, where Rp is hydrogen or lower

χ .lkyl;

R. = -lower alkylene, by halogen, alkoxy with preferably 1 · 6 carbon atoms or carboxy with preferably 1 - q carbon atoms, substituted lower alkylene, Cyclic alkylene with about 3-8 carbon atoms or phenylene; and

, in which.Ri vnä. R /. each for Vfessstoff ■. i

!; i ^Λ 4 are lower alkyl or lower alkyl substituted by amino or in which R ₇ and R / together with the? Stic «'» to ff atom to which they are bound form a three to three-membered, optionally saturated heterocyclic ring, which contains the nitrogen atom as the only one! ; e3 heteroatom or which contains a second heteroatom !: lus of the group: nitrogen, oxygen or sulfur. contains; . '- ·

-fj, where - £ ■) is a 3- to 8-part given-

.fallH represents saturated heterocyclic ring, which containing the *; nitrogen atom in the ring as the only heteroatom which contains a second heteroatom from the group: nitrogen, oxygen or sulfur; '. - -

* "d. unsaturated or saturated"'709825/0883 · "

·· Or-

- C - N-

$ ~ "C.-, where Rp- and R / - each represent hydrogen NH ^ ^R 6

or lower alkyl;

-N N-Ry-MHp »in which -N N-- stands for a 3- to 8-membered, optionally saturated heterocyclic ring which has the two nitrogen atoms as the only heteroatoms, and in which R _{7 stands} for lower alkylene;

or -SRg, where Rg is hydrogen or lower alkyl stands, · '

means;

or, when X has the above meaning and Y. = -N or

-SRg means R ^ represents those atoms that are necessary are to form a 3- to 8-membered, optionally saturated heterocyclic ring with X und.Y, the X and Y contains as the only heteroatoms;

- τι

and the quaternary ammonium s 3

salts of these when Y = N, in which R, and R /.

^ .R ₄ ³

represent lower alkyl; or the ternary sulfonium salts of these when Y is »-S-Rg, in which Rg represents lower alkyl. The quaternary ammonium or ternary sulfonium salts can be represented by the following formulas shown v / earth:

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¹ I ()

- CH

C = O

- _S T _{- Rc}

in which Hi

X and η have the same meaning as above,

. ,, R / and Rq lower alkyl, Rq an aliphatic group, like All 1, preferably lower alkyl, and A is an anion like eil, halide, sulfate, sulfonate, phosphate, hydroxide, nitrate,

Acetate see ode meaning

The hi · ¹ alkyls: · water

Paratoluenesulfonate or any other organir inorganic anion which can be used photographically,

• the terms "lower alkyl" and "lower" used

refer to straight or branched carbon offs chains with about 1 to 6 carbon atoms.

The present invention is illustrated by the accompanying drawings '"illustrates. They represent the following

The FiI silver

iren 1-31 are electron micrographs showing halide crystals in an amphoteric mixed polymer

Binders ptel, which according to Examples 12 - h2. Lst, show.

The amphoteric copolymers (I) according to the invention are water-3, film-forming copolymers obtained by reacting an on-cell reactant (II), H-X-R ^ -Y, where X, R ^ have the same meaning as above, with a mixed

(III) of maleic anhydride and an äthylenisch saturated, copolymerizable monomer, such as a in, styrene, N-vinylpyrrolidone or an alkyl vinyl ether, have been photographed. Maleic acid copolymers and their compounds

löSliC; bifunk * and Y

polymet unsst

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• 49-

positions are described in U.S. Patent 2,047,398. Some typical maleic acid copolymers (III) are as follows:

Mixed polymer

n-3utyl vinyl ether /
Maleic anhydride

n-butyl vinyl ether /
Maleic anhydride

Isobutyl vinyl ether / maleic anhydride

Isobutyl vinyl ether / maleic anhydride

Octadecyl vinyl ether / maleic anhydride

Isooctyl vinyl ether / maleic anhydride

Do de cylvinylether /
Maleic anhydride

C etyl vinyl ether /
Maleic anhydride

Styrene /
Maleic anhydride

Ethylene /
Maleic anhydride

Vinyl pyrrolidinone /
Maleic anhydride molar relative viscosity ratio in 1 % methyl ethylnis ketone

1: 1

1: 1 1: 1 1: 1 1: 1

2.2

1: 1 1.59 1: 1 3.93 1: 1 1.66 1: 1 1.91

1.91

■ 1.52

1.20

2.82

1.5: 1 2, 'iA (1 % in

N-methyl-2-pyrroli-

dinon)

1: 1

1.16 (1 % in H ₀ O)

Copolymers of maleic anhydride and an alkyl vinyl ether of the formula are particularly suitable:

*respectively. reissued as Ee 23-

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OR ¹

CH ₂ -Oh-CH- cn

where F;> = lower alkyl, preferably methyl, and the symbol η is a t Dsitive integer with a value of about 35 - 3500 significant These interpolymers generally have a mole ·. · kulargeticht from about 5000 - 500,000 and a specific one Viscosity between about 0.1 and 4 centistokes, preferably between about 0.1 and 2 centistokes (determined in a 196 Methyl ololly ketone solution), such as GAKTREZ AN-119 (specific Viscosity 0.1 - 0.5 centistoke), GANTREZ AN-139 (specific Viscosity 1jO - 1.4 Centistoke) and GANTREZ AN-I69 (specific t. viscosity 2.6 - 3.5), all from GAF Corporation, New Yoi, U.S.A.,.

The _amii;! Another mixed polymer (I) is made by reacting the bifunctionelü ^ n. Reactant (II) with the maleic anhydride: mixed polymer (ill) formed as follows:

(3 ) HX-R ₁ -Y + (III) 4S-CR CH -) - _n ^ (I)

= 0

CR C

C C

where Ik Rj j X> Y and η have the same meaning as above. The Re ^ i tion between the bifunctional reactant (II) uit ¹ the Maleinsäureanhydridmischpolymer (III) takes place in a <Q ganic solvent at an elevated temperature, for example from 40 ^{(^} to reflux temperature, easily occur, and there are no some particular conditions required. If the group Y in di amphoteric copolymer (I) is a primary amino group if, for example, Y = NRJEt ^, where R- and R ^ both stand for Wa., then the primary amino group should Y in

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ic.

the functional reactant (II) by a suitable one Protecting group are protected to initiate a reaction between the amino group Y and the maleic anhydride copolymer (III) to prevent »

Suitable bifunctional reactants, HX-R ^ -Y, are for example:

H ₉ N- (CH ₂ ) -N. ^ CH ₂ CH ₂ ,

H ₂ N- (CH ₂ ) ₃ -

-CH ₃ ;

, where χ = 1 - 6.

N-CH

CH ₂ - CH;

CH

H ₂ N

CH - CH ₂ - C COOH ^

-NI

HS- (CH- \ - Nr / where χ »1 - 6.

^ C

H ₂ N- (CH ₂ ) _x -S-CH ₃ , / wherein χ = 1-6.

i- (clL ·) _x - s - CH ₃ , ■ where χ is β- 1-6.

HO- (CH ₂ ) _x -

,; where x = 1-6.

μο - (CH 2 ) _x - S - CH ₃ , 1 "where χ» 1 - 6.

709825/088 3

H S-CH 2- Ν!

CH ₂

CH ₃

H ST-CH 2 -CH 2 " ^CH 2""" -CH ₂ -CH ₂ -CH ₂

H N-CH ₂ -CH 2 -CH jN

H N-CH- (CH ₂ ) 3 - NH - C - NH ₂ COOH NH

H; N-CH- CH ₂ - CH ₂ -S-, CH ₃
COOH

The qus ^ taren ammonium or ternary sulfonium salts of the amphotic s mixed polymer (I) can in all those cases in which Y in the formula (I) = -N ^ ^R 3 or SR ₈ - with R ₃ , R ^

and Rg =: i lower alkyl - means to be easily prepared, by cl ^ s amphoteric copolymer (I) with a suitable

solvents such as a lower alkyl halide, a halogenated acid, a methyl p-toluenesulfonate and the like. In such cases, the amphoteric mixture is mixed in a suitable solvent such as dimethylformam :. At an elevated temperature, for example of about .50 - 1OO ° C reacted with _S dei alkylating agent.

If d; fc amphoteric copolymer made from a bifunctional part Reactive participant (II) is produced, which is a primary Aminogy.ppe, e.g. if X = -NH-, it is It is possible that in addition to the amphoteric mixed polymer (I) also the foaming cyclic imide (Ic) as a secondary reaction product here is 11t:

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* υπ H

(Ic) - (- R- C C

.C = O

It is therefore preferred that the bifunctional reactants be have a secondary amino group as HX .., such as If-Methylpiperaain. Such a compound cannot have an imide structure form, and therefore have better control over the ratio of cationic to anionic functional groups During manufacture.

According to the invention, the photographic silver halide emulsions after the basic process of peptization and growth of silver halide grains by reacting a water-soluble alkali metal halide or a mixture of alkali metal halides with a water-soluble silver salt, for example silver nitrate, in an aqueous solution of the mixed polymer (I) of the invention or an aqueous solution of the mixed polymer (i) and gelatin or modified gelatin, such as a phthalyl derivative, are produced with stirring in the course of about 1 minute to 2 hours at a temperature of about 30 to 90 ^° C., preferably of about 50 to 70 ^° C. The liquid formed in the process Emulsion is made with an inorganic salt, as is the case with GelatineeTnuJsioner; used, for example ammonium sulfate or surface-active or polymeric sulfates and sulfonates, precipitated and. then acidified to a pH which is below the isoelectric point of the 'mixed polymer or mixed polymer / gelatine or modified gelatine carrier. Worth washed, it can be modified with gelatin, a

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Gelatiii and / 'or a gelatin-compatible substitute, such as zein, i ₅ bumin, cellulose derivatives, polysaccharides such as dextraii gum arabic and the like, or with such synthetic polymers as polyvinyl alcohol, acrylamides, polyvinylpyrrolidone and the like. earth »and the emulsion obtained is suitable for direct treatment before application to a suitable one

Carrier. 1.

The emissions can be caused by unstable sulfur compounds, such as sodium thiosulfate or thiourea; with reducing agent! ^ like tin-II-chloride; with salts of precious metals such as gold, ΙΊ. Lladium. And Platinum; or with combinations of these chemise sensitized.

The emissions can also be sensitized optically, for example ise with cyanine and merocyanine dyes. Possibly In addition to the emulsion composition, suitable anti-fogging agents, toners, retarders, developers * "i Development accelerators, preservatives, coating aids, plasticizers, hardeners and / or stabilizers !are given.

l

The emulsions according to the invention can be applied and processed by conventional methods. For example,> Le can access various types of rigid and flexible ■ Trägerrl such as glass, paper, metal, and polymeric films of both synthetic as well as type of species which have been produced from naturally occurring ^1, ι products are applied. Examples of special materials that can be used as carriers are: paper, aluminum, polyvinyl acetate, polyamides,> [le nylon, polyester, such as polymeric films made from

Ethyler5

Lycol-terephthalic acid, polystyrene,

Polycax · - 3nat and cellulose derivatives such as cellulose acetate, cellulose triacetate nitrate, propionate, butyrate, acetate propionate and acetate butyrate It has been found that these new Emulsic 2n according to the invention in a highly satisfactory manner on the supports be liable.

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As can be seen from the foregoing, the peptization, crystal growth and sensitization of the silver halide emulsion are carried out by conventional methods, and the optimal conditions are determined empirically using methods known to those skilled in the art. By using the mixed polymer (I) in the emulsion, however, are the properties the final emulsion, so that by controlling the various parameters associated with the copolymer (I) related, emulsions can be obtained as desired.

Excellent silver halide peptization and excellent Crystal growths are obtained when the molar ratio of the bifunctional reactant (II) to the maleic anhydride residues in the copolymer is between about 1: 1 and 1: 4. In other words, should the molar ratio of cationic groups to anionic groups in the amphoteric copolymer (i) is about 1: 1 to 1: 4 be. In general it has been observed that through a practically equimolar ratio of cationic to anionic Groups in the interpolymer, such as 1: 1 to 1: 1.1, the degree of peptization of the grains improves the formation of small ones Crystal sizes and a narrow distribution of these sizes favors as well as the speed of chemical sensitization increase. When the proportion of anionic groups is greater, for example at a molar ratio of cationic to anionic groups in the interpolymer from about 1r1.2 to 1: 1.5j then the growth of larger crystals will be with A wider size distribution is promoted, making one photographic Emulsions with higher photosensitivities and lower contrasts are obtained. When the proportion of anionic Groups becomes too large, e.g. with molar ratios of cationic to anionic groups of 1:> 4, then the crystals are incomplete peptized, the response to chemical sensitization is poor, and haze formation (especially the internal) is high.

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255488.2

A ι *.

iterate control over the molar ratio of cationic

to at. 'niche groups can be reached by using the mixed

polym ν one t given w.i the V: and i: «genomi :;

(i) a cationic surfactant with a lipatic chain of 8-18 carbon atoms. as described in U.S. Patent 3,113,026. Regarding the disclosure of this patent specification Application of surface-active cationic agents in particular to Table 1 is expressly referred to here • n. According to the invention, the surface-active

katio: 4 see agents optionally in an amount of up to about wt. %, based on the mixed polymer (I), used «It is possible to use: ¹ Ii all of the superactive agents listed in the patent mentioned; particularly suitable, however, are the compounds which contain guanyl and biguanido functional groups, for example the structures C-37 in Table I of US Pat That is, because many of the long chain surfactants containing guanido, biguanido or quaternary groups, etc., hung, can have adverse effects, ie, produce an undesirable crystal growth pattern, desensitization or fogging when used alone as photographic emulsions. However, if they are functional and in combination

are flat
Guani> C-27
and V more · to be bitten by an anion] having or '. call * 'added

are used with the amphoteric copolymer (I) according to the invention, they act as a means of controlling the cationic anion ratio. As explained in US Pat attributable to form könneJ and the inner salt or "zwitterion ¹¹ Equilibrium verses life can with the anionic Grupp- ι in the amphoteric copolymer (I) or the gelatin unlösJ. Lche salts (see US Patent 2,704,710), in order to generate a somewhat higher cationic-to-anionic ratio in the amphoteric copolymer (i) and / or gelatin layer which is absorbed by the silver halide grain surface.

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The amount of mixed polymer (I) required for silver halide peptization and for the growth of the grains is determined empirically; however, amounts of from about 1.0 to 70 grams per mole of silver halide are generally satisfactory. If too small an amount of the mixed polymer (I) is used, there is a risk that the silver halide grains will be incompletely dispersed and the applied, exposed and developed emulsions will then look "speckled". If an excessively high concentration of the mixed polymer (I) is used, it may be difficult to properly precipitate or coagulate and wash the emulsion when. such trouble occurs, it is easy to change the proportion of the mixed polymer to obtain satisfactory results.

The gelatin can be mixed with the amphoteric mixed polymer (I) before and / or after the peptization and grain growth stage. Since the mixed polymer is compatible with gelatin in all proportions, it is possible to use the mixed polymer (I) and gelatin in any required ratio in order to obtain the desired photographic properties. The only thing that should be taken into account is that at a high concentration of either the copolymer or the gelatin, physical difficulties can arise during the precipitation and subsequent ashing of the emulsion. The gelatin can be used, for example, in an amount up to about 2500%, such as from about 2 ₅ 5 to 2500 %, based on the weight of the mixed polymer (I), either during the Pept. 1 safety and grain growth stage or after »

The following examples serve to explain the present in more detail Invention. All parts and ratios given are based on weight, unless otherwise stated.

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Example € ^! JL

I herste! ong from:

'H °° ^Η 3 -iCI - CH - CH - CH

CH -) -

GOH C - NH - {CII.

CH ₃

ψ - CH ₃ * CH ,,,

CH ₃

A heated mixture of 15.6 g (0.1 mol) of a methyl vinyl

ether-Ii 40.8 g -ν benzene «to 80 ^C y solid 1: washed angerχc exsikki

leinsäureanhydrid mixed polymer (Gantrez AN-119) and D, 4 mole) of 3-dimethylaminopropylamine in 82 ml of dry ar de 4 hours at 50 - 55 ⁰ C and 1/2 hour

heated. The mixture was then cooled and the material was removed by filtration and washed with benzene n. The filter cake was washed with anhydrous diethyl ether

en

removed by filtration and placed in a vacuum

or dried. Yield: 32.5 g.

The polymer has been purified (i.e. from the 3-dimethylaminopropylamine salt) freed, which is partially released as a secondary reaction product) by dissolving it in water and passing it through a column

formed escort;

was the

Dowex 50 ¥ XB ion exchange resin

The aqueous solution of the polymer was evaporated to dryness under reduced pressure.

A solution of 6.3 g of the polymer purified above and 4.7 g of Ii thyl p-toluenesulfonate in 25 ml of dimethylformamide was Heated for 4 hours over a steam bath. The cooled Solution was then poured into diethyl ether, and the resulting Gumn-like precipitate was rubbed and decanted ren washed with diethyl ether.

The above !:. Dried quaternized polymer weighed 8.8 g and had the structure shown above.

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Production of:

OCH ₃

4CIl ₂ - CH - CH - CH - CH) I η.

COOH

= 0 CH ₃

NH- (CH-). - }

2'3

- CH ₂ COOH Br "

CH ₃

Following the same procedure as in Example 1, but using bromoacetic acid as the alkylating agent, was prepared the above copolymer.

Example 3
Production of:

f «3 j

, - CH - CH - CH -t i

η I

COOH j / 3

~ - OCH ₀ CH ₀ -Γ

-H ₃

A stirred solution of 35.6 g (0.2 k mol) of 2-dimethylaminoethanol in 750 ml of acetone slowly became a solution of 63 g (0.4 mol) of a methyl vinyl ether-maleic anhydride mixed polymer (GANTREZ AN-119) in 750 ml of acetone added at the reflux 'temperature of acetone. Then 5 drops of concentrated sulfuric acid were added and the whole was refluxed for about 12 hours. The precipitated material was removed by filtration and washed with acetone. The amphoteric polymer shown above was recovered in a yield of 98.6 g.

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B ei sp

Manufacture of:

In a hurry; gesture N-Met * to zl

POLYNV EQUIPMENT.

The c ^ and c L

salts!

derive

(J) CH ₃ (CH ₂ - CH - CH - CH)

COOH

η C - N

CH

-CH

CH

N CH-

2n 2-liter flask fitted with a mechanical stirrer, reflux condenser and dropping funnel a solution of 27.2 g (0.272 mol) of flpiperazine in 600 ml of acetone was added. The solution was α refluxed, and then a solution of 50 g was in the course of iten through the dropping funnel iol) of a methyl vinyl ether-maleic anhydride mixture " rs (GANTREZ AN-119) in 600 ml of acetone was added. the te mixture was refluxed for 16 hours, 3precipitated solid was removed by filtration, the filter cake was washed with acetone until the ■ solutions were free of yellow color. The air-dried material, that from a mixture of N-methylpiperazine- = the free acid and the N-methylpiperazinecarboxamidefc of the methyl vinyl ether-maleic acid "Dlymer described above, weighed 77" 2 g "

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Example 5

- Φι io>

Production of:

4 CH- CH - CH-

-CH

OOH

CON

A mixture of 77.2 g of the interpolymer from Example 4 (containing about 0.272 moles of tertiary amino groups), 56 g (0.3 moles) of methyl p-toluenesulfonate and 400 ml of dimethylformamide was placed in a 2 liter flask and heated with stirring to a temperature of 90-95 ^° C. for 7 1/2 hours (after an initial exothermic reaction). Then the response was ?; mixture poured into 2 liters of acetone. The resulting precipitate was stirred for 11/2 hours and the acetone was removed by decantation. Fresh acetone was added to the solid and the slurry was again stirred for 1 1/2 hours. The product was removed by filtration and washed with acetone. The air-dried quaternized polymer weighed 105 g.

Example 6 Production of:

OC ₄ H ₉ -f CH ₂ - CH - CH

CH CH Y

COOH> - "·>

ι /

con

'CH-j-

-CH.

-CH

"CH

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The obi \ '2 N-methylpiperazine carboxamide derivative of the butyl vinyl ether-Ml ¹ ' .einic acid mixed polymer was prepared in the same manner as in Examples 4 and 5, with GANTREZ ?; instead of GANTREZ ?; 1-119 a butyl vinyl ether-maleic acid copolymer (relative viscosity in 1 % methyl ethyl ketone = 1.59) was used.

Example J _7

Herstel!; mg of:

The obiJ process ί vinegars

2 amphoteric copolymer was made according to the same ι as in Example 5, but using Bromre as an alkylating agent.

Example | _8th

Manufacture of:

OCH.

Γ

, - CH - CH-

COOH

H

COOH

CH ₂ -C

A chloricf was ί'ι vinyläi II in 200

stirred solution of 39.9 g (0.2 mol) of L-histidine monohydrolydrate and 40.4 g (0.3 mol) of triethylamine in 300 ml of water dropwise a solution of 31.2 g (0.2 mol) of a methylsr-maleic anhydride copolymer (GANTREZ AN-119) 1 dimethylformamide was added and the whole was

709825/0 8

Heated over a steam bath for 8 hours. The cooled Solution was then poured into 2 l of acetone, and the resulting gummy precipitate was decanted off with Acetone washed. The semi-solid material was made with absolute Rubbed ethanol, removed by filtration and dried in vacuo. The above copolymer was obtained in one yield of 62.5 g.

Example 9

Production of:

OCH ₃
-f CH ₂ - CH - CH CH> _n

COOH C-NH- CH-

C0ÖH

A heated solution (90-95 ° C) of 42 g (0.2 mol) of L-arginine hydrochloride and 1.5 g of sodium hydroxide in 50 ml of water and 100 ml of dimethylformamide slowly became a solution of a methyl vinyl ether-maleic anhydride copolymer (GANTRSZ AN-119) in 250 ml of dimethylformamide was added, and the whole thing was heated over an ¥ water vapor bath for about 16 hours. The cooled mixture was then poured into 2 liters of acetone and the solid material that precipitated was removed by filtration removed. The product was ground in a blender with acetone, then removed again by filtration and washed with acetone « The yield of the above copolymer was 65 g.

Example 10

Production of: . . .

OCH ₃

• f CH ₂ - CH - cn CH t _n

COOH C - NH - CH - CH ₀ - CH ₂ - S - CHi '

Il

0 COOH

7098 2 5/0883

A: j acid »r; shape; one: 8.0, · .. off
After C sich -ij Lösui

with
was washed; [dr; booty

■ ⁱ i

In d :; Reak ύ Bild'i tion ljj anio ι.? prim \ enth. spie; ¹ ] Stru

dissolution of 15.6 g (0.1 mol) of methyl vinyl ether Maleinnhydrid mixed polymer (Gantrez AN-119) in 100 ml Diinethylid was at a temperature of 35-40 ⁰ C slowly stirred solution of 29.8 g (0.2 Mol) DL-methionine and (0.2 mol) sodium hydroxide in 300 ml of water were added, and a white solid was precipitated out of the reaction mixture. Heating over a steam bath for about hours had completely dissolved the solid material. The cooled was then poured into 3 liters of acetone, and the rubbery blow that had precipitated was washed by decanting ashes acetone until it solidified. The product is removed by filtration, mixed with anhydrous acetone, ground to a fine powder and kneaded under vacuum. The above copolymer was obtained in an amount of 46.5 g.

L Examples 8, 9 and 10 contain the bifunctional ' .on participants a primary amino group, so that the ig the cyclic imide structure (Ic) as a secondary reaction »Roduct is possible. These structures would still have both .se and cationic groups due to the in that • en amino reactants present carboxy group. The cyclic imides that are involved in the reaction of the two > 8 to 10 are formed, would therefore have the following; uren 8 'to 10':

C8 ¹ );

HOOC-CH-CH ₂ -C

OCH

Ο ¹ )

HOOC-CH (Qi ₂ ) ₃ -NH-C-NU ₂ OCH ₃ H

-CH -

Hooc

- αϊ-

(10) I.

au- au- s - cn

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Example 11
Production of:

-f CH -, - CH - CR-

Br '

A stirred solution of 15> 8 g (0.2 mol) of imidazo! in 50ml Acetone slowly became a solution of 15.6 g (0.1 mol) of a methyl vinyl ether-maleic anhydride mixed polymer (GANTREZ AN-119) in 110 ml of acetone was added * and the whole thing was 8 hours long "at room temperature. The acetone was through Decant off the semi-solid precipitate, and the gummy residue was washed with anhydrous ethyl ether rubbed until it solidified. The vacuum dried material weighed 22.9 g.

A solution of 22 g of the above product in 100 ml of dimethylformamide was slowly treated with a solution of 24.1 g (0.18 mol) of bromoacetic acid in 25 ml of dimethylformamide and the mixture was heated over a V-steam bath for 3 hours. The cooled solution was then poured into acetone, whereupon an oily material was precipitated. The acetone was removed by decanting and the oily residue was rubbed with petroleum ether (boiling point 30-60) until it solidified. The vacuum-dried polymer weighed 3 g.

Examples 12-42

In the following Examples 12-42, the following Method A or B described. Silver halide photographic emulsions both with and without the addition of a cationic surfactant. In table I are the emulsion production process used, the silver

709825/0883

halide content of the emulsion and the amount and type of mixed polymer and the cationic surfactant. hears. The structures of the surfactants are in act He II listed.

The EmuXpionsherstellungsverfafrren A and Table I mentioned. B are the following:

Γι Ί

Emuls: ^ manufacturing process A

Ϊ, Te: '__I ^H 2 ° ^{= 10} ° ^ml

KBr a 36 - 50 g

Ko = 0.5 -7g

Ann '(2Ci

Ka-

other mixed polymer (I)

solution in H ₂ O) = 2 - 100 ml

onic surface-active el (i # solution in H _? 0 or methanol) = 0 - 50 ml

The pH value is adjusted to 3.5 - 6.0 (for example with 1n Na (I or Na ₂ CO- ^ or 1n H ₂ SO ^, depending on the initial pH-We:).

Te: 'II H ₀ O = 500 ml

Te. III H ₂ O = 25 ml

AgNO ₃ »50 g

H ₂ O = 25 η gelatin = 5 g

vrird part I at a temperature of 50 - 70 ⁰ C and; on from 1 minute to 2 hours (depending on the desired

Part: in Ve:

Krist '! Sizes) added.

Danac. ' the gelatin solution from Part III is added.

Then 'around the whole cooled to 40 ⁰ C.

Now a precipitation occurs with 300-500 ml ammonium sulfate (50%)

bewir::.

709825/0883

The precipitated product is washed four times by decanting.

The washed, precipitated product is mixed with 64 g of gelatin (or another gelatin-compatible polymer) in 350 ml Water restored c

Finally, enough water is added to make 800 g a non-sensitized emulsion.

Emulsion Making Process B

Part I H ₂ O = 100 ml

KBr = 36 - 50 g, Kj = 0.5 - 7 g Gelatin = 0.5 ~ 10g

Amuhoteric polymer (l)

(20% solution in H ₂ O) = 2-100 ml

Cationic surfactant (15% solution in H ₂ O

or methanol) ~ 0 - 50 ml

The pH is adjusted to 3.5-6.0 (for example with In NaOH or Na.pCO, or 1n HpSOy ₄ , depending on the initial pH).

Part HA 'H ₂ O = 500 ml

AgNO ^ = 50 g

The procedure is the same as for method A, but part ■ becomes III, the gelatin, is omitted.

The emulsions prepared by processes A and B of the Examples 12-42 are sensitized to optimum photosensitivity and gradation, which is due to the Crystal size and distribution is determined by the usual method using those described above Sensitizers.

709825/0 883

Tabel

FIg, example .Emulsions Photographic emulsion HOJ. WOX Mixed polymer u-ew./ 1 12th procedure MOl %% 50 g 2 13th A. AgBr AgCl AgNO,
2.5g 3 14th A. 92 example 2.5 4th 15th Λ 8th 92 1 5.0 5 16 A. 8th 90 2 5.0 6th 17th Λ 10 90 3 2.5 7th 18th A. 10 90 4th 5.0 -J 8th 19th A. 10 90 5 5.0 O 9 20th A. 10 92 6th 10.0 co 10 21 A. 8th 92 7th 2.5 co 11 22nd A. 8th 92 8th 5.0 12th 23 A. 8th 92 9 1.5 cn 13th 24 A. 8th 92 10 2.5 CD 14th 25th A. 8th 95 3 11 5.0 00 15th 26th A. 2 95 1 5 2.5 OO 16 27 B. 4th 90 6 5 2.5 c *> 17th 28 B. 4th 90 5 2.5 IS 29 B. 10 90 5 2.5 19th 30th B. 10 100 5 2.5 20th 31 B. - 98 5 2.5 21 32 B. 2 98 5 2.5 22nd 33 B. 2 98 5 2.5 23 34 B. 2 90 5 2.5 24 35 B. 10 90 5 2.5 25th 36 B. 10 90 5 2.5 26th 37 B. 10 98 5 2.5 27 38 B. 2 98 5 2.5 28 39 B. 2 98 5 2.5 29 40 B. 2 90 5 2.5 30th 41 B. 10 90 5 2.5 31 42 B. 10 90 5 2.5 B. 10 98 5 2.5 2 90 5 10 5

Cationic surfactant

structure

No.

115
115
115
115
115
115
115
115
116
117
113
118
119
120
121
121

0.04 0.04 0.04 0.04 0.04 0.01 0.10 0.20 0.20 0.20 0.05 0.10 0.05 0.12 0.06 0.06

• CO CO IO

120

Table II Cationic Surfactants

structure

No structure

C II NH -C- NH ,. I ^ 2 D Il ^

115

C II NH I ^ 2 D

ITO ¹¹⁶ ^

~ ^C

NH

¹¹⁷ C, _O H_ _C ? IH - C - NH - C - NH, .CH, jäSQ "H

1- 25 j. I ₃₁

NH NH CH.

¹¹⁸ C ₁₅ H ₃₁ CONH - ψ - CH ₃ -CH ₃ OSO ₃

CH 3

CH3 j

¹¹⁹ C ₁ ΛΙ. _Λ CONH- (CH-). - ft - CH _v CHJ2fe0

CH ₃

CH ₃

C ₁ -H CQMH-CH CONH- (CH ₉ K-N-CH <CH 1/35 ^ I 3

3 CH ₃

TOT "■ J" 4 *

121 CH SO - (CH) -N -

CII,

709825/0883

-25-

For (■ He emulsions of Examples 12-42, electron technology: i; photographs were made, which are shown in FIGS. 1-31. The crystal size and the size distribution of these emulsions can be seen from these figures Magnification of _<; 0.000 X her ^ e-jte.llt, ur> d in 6.u / j Fi ^. 1 - 31 six *? · Diasc KiIc !; photographs reduced by etv / a 1/3. To read In Fig. 1, the scale ang ii is flat, and the other figures 2-31 have the same dimension i ab.

709825/0883

Claims (22)

Patent claims: 1. "Photographic silver halide emulsion, characterized in that that the emulsion binder comprises a water-soluble, film-forming, anrphoteric copolymer which is im Molecule repeating units of general Formula: ⁰ I. has, wherein η ~ a positive integer - R - the remainder of an ethylenically unsaturated organic monomer; χ _Α -H-, -S- or -0-, where Rp is hydrogen or nie.de-I res alkyl; R ₂ R. = lower alkylene, through halogen, alkoxy or carboxy substituted lower alkylene, cycloalkylene of about 3-8 carbon atoms, or phenylene; and > ^R 3
Y - -N, where R ^ and R _h each for V / ate he material, 4 lower alkyl or substituted by amino. tuierte lower alkyl or in which R-, and R. together with the nitrogen atom to which they are attached a 3- to 8-membered, optionally saturated heterocyclic Form a ring which contains the nitrogen atom as the only heteroatom or which contains a second heteroatom from the group: nitrogen, oxygen or sulfur contains, / C \. C \ j
4-; , where + - ) \ is a 3 to 8-part given- if represents a saturated heterocyclic ring, which contains the nitrogen atom in the ring as the only heteroatom 7098 ^ 5- / 4) 863. ... ".. 'V holds or which contains a second heteroatom from the group: nitrogen, oxygen or sulfur, - NH - C - N ^ _v ^: where R ₁₅ and R 1 - each represent hydrogen or lower alkyl _f -N N-Ry-NH ₂ , where -N N- is a 3- to 8-membered, optionally saturated heterocyclic ring which has the two nitrogen atoms as the only heteroatoms, and where Ry is lower alkylene, or -SRg, where R _{Q is} hydrogen or lower alkyl, means; or, when X has the above meaning and Y = -N or -SRq, R ^ represents those atoms necessary membered 8 form a 3- to, optionally saturated heterocyclic ring having X and Y to form the X _t and Y contains as the only heteroatoms; i are the quaternary ammonium salts of these when Y = H _x denotes where R ^ and R <are lower alkyl; or ternary sulfonium salts of these, if Y = -S-Rg, wherein R _g is lower alkyl. 2. Emulsion according to claim 1 _; characterized in that the emulsion binder comprises gelatin or a modified gelatin. 3. Emulsion according to claim 2, characterized in that the gelatin or modified gelatin in an amount up to about 2500% by weight based on the weight of the amphoteric Mixed polymer, is present. 709825/0883 > 654882 4. Emulsic | according to claim 1-3, characterized in that η means a fmze number from about 20 to 5000. 5. Emulsio according to claim 1-4, characterized in that OR ¹ ■ ^j R - -CH | -CH- - rait R ¹ = lower alkyl - and η = one whole Z fil mean from about 35 to 3500. 6. Emulsio | according to claim 5, characterized in that R '= Me |: yl or η-butyl. 7. Emulsio das amp 1.0 - 7 according to claim 1-6. characterized in that tere copolymer in an amount of about g per mole of silver halide is present. 8. Emulsio you an aliphatic proof on the according to claim 1-7, characterized in that surface-active cationic agent, the one before chain with about 8-18 carbon atoms in an amount up to about 5 wt. ~%, based mphoteric copolymer. 9. Kmulsio: according to claims 1-8, characterized in that at least I s a part of the repeating units the B ⁿ orj 11: 4R- on white alkylene in app: wherein R ,. = lower substituted by carboxy and R, Y and η have the same meaning as ch 1. 709825/0883 10. Emulsion according to claim 1, characterized in that the araphoteric copolymer has the formula: QCH- KH ₂ -CH - CH - CH Y _n CH ₃ : OOH C-TIH- (CH ₉ ) -, - 1I ⁺ -CHo. CH, O SO, "O CH 3 CH 3 HOOC - (CH ₂ -CH -CH-CH-CH) -HOOC ' C = O <Χ ^Η 3 I ₂ I 3- ^ HH- (CH ₉ ) ₃ -ljl ⁺ -CH ₉ COOII Br " H -fCH OCH ₃ 1 — CH * CH - 0OH C - OCH ₉ CH ₂ -N ₂ -CH -QH- CII) _n OOII cn cn C-N CH 3 » QCH. i CH ₂ -CH - CH CH) - COf 0OH CH- CH ^ CH ₃ 709825/0883 pC4 ^H 9 - (CH ₉ -CH - CH CHf I COOH CON in , CH. -CH 3 CH ₃ JJfSO ₃ OCH ₃ - (CH ₂ -CH - CH- CHf _n COOH CIIr N ⁺ '"2 CH ₂ COOH OCII ₃ > -CH - CH- COOH CHh 0OH C-NH- COOH OCH ₃ - (CH ₂ -CH - CH : 00H C-NH-CH- (CH ₂ ) 3-NH-C-NH. ! 0OH OCH ₃ - (CH, -CH - CH CHf _n COOH C C-HH-CH-CH ₂ -CH ₂ -S-CH. i A 709825/0883 OCH ι Br "COOH Ii \ I auiwezst ;. 11. A method for preparing a silver halide photographic emulsion, characterized in that it is the reaction of a water-soluble silver salt with a water-soluble alkali metal halide in an aqueous solution of a water-soluble, fUmbildende, amphoteric Mixed polymer, which in the molecule has repeating units of the general formula: CH CH f i η o = c ς = ο ι has, wherein η, R, X, R ^ and Y have the same meaning as in claim 1, - comprises. 12. The method according to claim 11, characterized _f that the aqueous solution contains gelatin or a modified gelatin. 13. The method according to claim 12 »characterized in that the gelatin or modified gelatin in. An amount up to about 2500 wt .-%, based on the weight of the amphoteric mixed polymer is used. 709825/0883 14. VfCj drive according to claim 11-13, characterized in that η means an integer between about 20 and 5000. 15. Vf drive according to claim 11-14, characterized in that OR ' I.
Ri] -CH ₂ -CH- - with R '= lower alkyl ■ - and η a whole Zi 1 mean between about 35 and 3500. "ι 16. Vf drive according to claim 15, characterized in that R = methyl or η-butyl * 17. Vfu drive according to claim 11-16, characterized in that d <amphoteric copolymer in an amount of about 1.0 7 ( g per mole of silver halide is used. 18. Vfv! drive according to claim 11-17, characterized in that d: 1: aqueous solution a surface active cationic M: -itel, which is an aliphatic chain with about 8-18 KcÖ! 1 ens toff has atoms, in an amount up to about 5% by weight, based on the amphoteric copolymer. 1.1 19. Vf'j drive according to claim 11-18, characterized in that Wf V at least a part of the repeating units the Fc rael: O = C _x au has in which R = substituted by carboxy η: ί which is alkylene and R, Y and η are the same Requirement as in claim 11 * 709825/0883 20. The method according to claim 11, characterized in that an aniphoteric copolymer of the formula: OCH- - (CH ₂ -CH - CH - CH - CH> _n COOH C - II X + UU - (Cn ₂ J ₃ -N- CH ₃ -CH CH-, OCH ₃ -4CH ₂ -CH - CH - CH - Cftt- _n COOH C = »0 NH- CH- CH. COOH Br OCH ₃ , -CH - CH - C C 00H C - OCH ₂ CH ₀ -T CH- H. OCH ₃ -iCE ₂ -CE - CH -00H CH ₀ CH ² \ N CII J, ■ 3 y OCH ₃ - (CH ₂ -CH - CH CH ^ ₁ TT CH COOH / CON ^^ CH CH -CH ₃ CHJiSO ₃ "':, 709825/0883 ■] OC ₄ H ₉ CHo-CH - CH CHK COOH • \ CH - M ^0CH 3 , -CH- -CH ₇ -CH- CH CH -) - OOH CON / N ^ X ^Br ' ' ^X CH ₂ COOH OCH ₃ - CH CHt _n I ' COOH C-NH- CH CH ₀ - C == Il - i ² I. COOH? L NH y / OCH ₃ - (CH ₂ -CH - CjH-CHt _n COOH C-NH-CH - (CH.,)., - NH -C- H j Δ Λ Il CC iOOH NH ? ^CH 3 : H - CH CHh _n COOH C - NH - CH - CH ₀ - CH ₀ - S-CH-COOH or OCH 3 fCH _o -CH - CH CHK CH = N ^T -CH _o CO0H Br ' ί II Il / ι £. COOH C Ν · ^ CH = CH is used. 9 8 25/0883 21. Emulsion according to claim 8, characterized in that the surface-active cationic agent from the group: C ₁₂ H ₂₅ NH - SfH C ₁₂ H ₂₅ NH -C -NH-C-N NH C ₁₅ H ₃₁ CONH-N-CH ₃ CH, ³ CH C ₁₅ H ₃₁ CONH - (CH ₂ J ₃ - N ⁺ - CH _3. CH ₃ OSO ₃ 3 CH ₃ C ₁₇ II ₃₅ CONH - CH ₂ CONH- (CHp) ₃ Ti ⁺ -CH CII _{3 3} C ₁₆ H ₃₃ SO ₂ - (CII ₂ ) 3-N ⁺ - CH ₃ . CH ₃ OSO ₃ " _f CH ₃ is chosen. 709825/0883 265A882 22. Vtii drive according to claim 18, characterized in that e: cationic surfactant selected from the group; ^C 12 ^H 25 ^NH - I - ^N V ^{C! I} NH -NH -C- NH ₂ -CH ₃ ^ SO ₃ H, NH C ₁₂ H ₂₅ NH - C - NH - C - NH ₂ -CH ₃ (JSO ₃ H, NH NH CH3 C ₁₅ H ₃₁ CONH - N ⁺ - CH ₃ .CH 0SO ₃ , CH ₃ f C ₁₅ H ₃₁ CONH - (CH ₂ ) ₃ - N ⁺ - CII ₃ CH ₃ C ₁₇ H ₃₅ CONH - CH ₂ CONH- (CII ₂ ) 3 N ⁺ -CH ₃ -CH ₃₁ JiSO ₃ , Ί7 "35 9 ^H 3 CH ₃ f ⁺ - CII ₃ CH ₃ ν ^ is applied. 709825/0883